Ammonium and iminium compounds

ABSTRACT

Ammonium compounds of the formula (I) ##STR1## in which at least one of the radicals R 1  to R 4  denotes a fluorine-containing alkyl radical having 4 to 30 carbon atoms and not more than three of the radicals R 1  to R 4  independently of one another denote hydrogen atoms or alkyl or hydroxyalkyl radicals having 1 to 30 carbon atoms, and R 5  to R 8  denote aryl, alkylaryl or halogenoaryl radicals or fluorine atoms, and iminium compounds of the formula (II) ##STR2## in which Q, together with the constituent ##STR3## forms a ring system having 4 to 17 carbon atoms, which can be interrupted by 1 to 4 hetero atoms and contain 2 to 9 double bonds, and which can be substituted by fluorine, chlorine, bromine or iodine atoms or alkyl (C 1  -C 6 ), alkoxy (C 1  -C 6 ), nitro or amino groups, R 9  denotes a fluorine-containing alkyl (C 1  -C 30 ) radical, R 10  denotes a hydrogen, fluorine, chlorine, bromine or iodine atom or an alkyl(C 1  -C 6 ), alkoxy (C 1  -C 6 ), nitro or amino group and the radicals R 11  to R 14  denote aryl radicals, alkylaryl radicals, halogenoaryl radicals or fluorine atoms, and mixtures of these compounds and processes for their preparation.

The present invention relates to novel ammonium and iminium compounds and processes for their preparation.

The present invention specifically relates to novel ammonium compounds of the general formula (I) ##STR4## in which at least one of the radicals R₁ to R₄ denotes a straight-chain fluorine-containing unsaturated and/or saturated alkyl radical having 4 to 30 carbon atoms and not more than three of the radicals R₁ to R₄ independently of one another denote hydrogen atoms or straight-chain or branched alkyl or hydroxyalkyl radicals having 1 to 30 carbon atoms, and R₅ to R₈ denote aryl radicals, such as, for example, phenyl or naphthyl radicals, and furthermore alkylaryl radicals, such as, for example, the toluyl radical, halogenoaryl radicals, such as, for example, fluorophenyl or chlorophenyl radicals, or fluorine atoms, and to mixtures of these compounds, and iminium compounds of the general formula (II) ##STR5## in which Q, together with the constituent ##STR6## forms a mono- or polynuclear ring system having 4 to 17 carbon atoms, which can additionally be interrupted by 1 to 4 hetero atoms, such as, for example, nitrogen, oxygen or sulfur atoms, and contain 2 to 9 double bonds, and which can be substituted in any desired position by fluorine, chlorine, bromine or iodine atoms or alkyl(C₁ -C₆), alkoxy(C₁ -C₆), nitro or amino groups, R₉ denotes a fluorine-containing alkyl(C₁ -C₃₀) radical, R₁₀ denotes a hydrogen, fluorine, chlorine, bromine or iodine atom or an alkyl(C₁ -C₆), alkoxy(C₁ -C₆ ), nitro or amino group and the radicals R₁₁ to R₁₄ denote aryl radicals, such as, for example, phenyl or naphthyl radicals, alkylaryl radicals, such as, for example, the toluyl radical, halogenoaryl radicals, such as, for example, fluorophenyl or chlorophenyl radicals, or fluorine atoms, and to mixtures of these compounds.

The invention particularly relates to those compounds of the abovementioned general formula (I) in which at least one of the radicals R₁ to R₄ denotes a straight-chain fluorine-containing unsaturated and/or saturated alkyl radical having 4 to 14C atoms and not more than three of the radicals R₁ to R₄ independently of one another denote straight-chain or branched alkyl(C₁ -C₄) or hydroxyalkyl(C₁ -C₄) radicals, and R₅ to R₈ denote phenyl, naphthyl, p-chlorophenyl or p-toluyl radicals or fluorine atoms, and to compounds of the general formula (II) mentioned, in which Q, together with the constituent ##STR7## forms a mono- or polynuclear ring system having 4 to 10 carbon atoms, which can additionally be interrupted by 1 to 4 hetero atoms, such as, for example, nitrogen, oxygen or sulfur atoms, and contain 2 to 5 double bonds and which can be substituted in any desired position by fluorine, chlorine, bromine or iodine atoms or alkyl(C₁ -C₆), alkoxy(C₁ -C₆), nitro or amino groups, R₉ denotes a fluorine-containing alkyl(C₄ -C₁₄) radical, R₁₀ denotes a hydrogen, fluorine, chlorine, bromine or iodine atom or an alkyl(C₁ -C₆), alkoxy(C₁ -C₆), nitro or amino group and the radicals R₅ to R₈ and R₁₁ to R₁₄ denote phenyl, p-chlorophenyl, p-toluyl or naphthyl radicals or fluorine atoms, and to mixtures of these compounds.

The invention especially relates to compounds of the abovementioned general formula (I) in which at least one of the radicals R₁ to R₄ denotes the group --CH₂ --CH═CF--Rf (Rf=C₅ F₁₁ --C₁₁ F₂₃), the group --CH₂ --CH═CF--C_(n) F_(2n+1), where n=5, 7 or 9, or the group --CH₂ --CH═CF--C₇ F₁₅, and not more than three of the radicals R₁ to R₄ independently of one another denote a methyl, ethyl, butyl or hydroxyethyl group, and to compounds of the abovementioned general formula (II) in which Q, together with the constituent ##STR8## forms a pyridine, pyrazine or quinoline ring system, R₉ denotes a C₈ F₁₇ --CH₂ --CH₂ -- group, R₁₀ denotes a hydrogen atom and the radicals R₅ to R₈ and R₁₁ to R₁₄ denote phenyl, p-chlorophenyl, p-toluyl or naphthyl radicals or fluorine atoms, and to mixtures of these compounds.

The following may be mentioned as examples of individual compounds or mixtures of compounds of the general formulae (I) or (II): ##STR9##

The ammonium or iminium compounds and mixtures of ammonium or iminium compounds of the general formulae (I) or (II) mentioned can be prepared by reacting the ammonium compounds and mixtures of ammonium compounds of the general formula (III) ##STR10## in which at least one of the radicals R₁ to R₄ denotes a straight-chain fluorine-containing unsaturated and/or saturated alkyl radical having 4 to 30 carbon atoms and not more than three of the radicals R₁ to R₄ independently of one another denote hydrogen atoms or straight-chain or branched alkyl or hydroxyalkyl radicals having 1 to 30 carbon atoms, and X⁻ denotes a halogen anion, for example a chlorine, bromine or iodine anion, or a methylsulfate anion, and by reacting iminium compounds or mixtures of iminium compounds of the general formula (IV) ##STR11## in which Q, together with the constituent ##STR12## forms a mono- or polynuclear ring system having 4 to 17 carbon atoms, which can additionally be interrupted by 1 to 4 hetero atoms, preferably nitrogen, oxygen or sulfur atoms, and contain 2 to 9 double bonds, and which can be substituted in any desired position by fluorine, chlorine, bromine or iodine atoms or an alkyl(C₁ -C₆), alkoxy(C₁ -C₆), nitro or amino group, R₉ denotes a fluorine-containing alkyl(C₁ -C₃₀) radical, R₁₀ denotes a hydrogen, fluorine, chlorine, bromine or iodine atom or an alkyl(C₁ -C₆), alkoxy(C₁ -C₆), nitro or amino group and Y⁻ denotes a halogen anion, for example a chlorine, bromine or iodine anion, or a methylsulfate anion (the synthesis of the compounds of the general formulae III and IV mentioned is described in U.S. Pat. No. 3,535,381, German Offenlegungsschrift 1,922,277, German Offenlegungsschrift 2,244,297 and German Offenlegungsschrift 3,306,933), with a borate salt in water or mixtures of water and organic solvent, such as, for example, isopropanol, isobutanol or methyl isobutyl ketone, at temperatures from about 20° C. to about 90° C., preferably from about 50° C. to about 80° C.

The compounds and compound mixtures of the general formulae (I) and (II) are obtained in a good yield and purity by this process and can be isolated directly from the reaction medium by filtration.

Thus, for example, the above compounds of the formulae (1) to (14) are prepared by reacting the starting compounds (15) to (21) below ##STR13## with sodium tetraphenylborate, sodium tetra-p-chloro-phenylborate, sodium tetra-p-toluylborate or sodium tetrafluoroborate see the following Preparation Examples 1 to 6). Sodium tetra-p-chlorophenylborate and sodium tetra-p-toluylborate were prepared in accordance with the instructions of H. Holzapfel and C. Richter, J. Prakt. Chem. 26 (1964), 15-23. The ammonium and iminium compounds according to the invention are outstandingly suitable for use as charge control agents in electrophotographic toners and developers for electrophotographic recording processes.

The preparation examples below serve to illustrate the invention without limiting it to these.

PREPARATION EXAMPLE 1

160 ml of water are added to 40 ml of a 0.5 molar aqueous solution (0.020 mol) of the compound of the above-mentioned formula (15) (molecular weight 672) and 22 ml of a 1.0M aqueous solution of sodium tetraphenylborate (0.022 mol) are then added dropwise over a period of 15 to 20 minutes, while stirring vigorously. The mixture is made up to 500 ml with water and heated to 50° C. and the thick white precipitate is filtered off hot with suction. The product is washed thoroughly with water and dried at 50° C. in a circulating air cabinet.

    ______________________________________                                         Yield          16.9 g (96.0% of theory) of the                                                compound (1)                                                    Molecular weight                                                                              880                                                             Melting point  154-156° C.                                              Elemental analysis                                                                            calculated 4.1% H, 1.6% N, 1.2% B                                              found 4.1% H, 1.6% N, 1.1% B,                                                  0.05% water                                                     1H-NMR (in DMSO-d6)                                                                           1.20 (triplet, 6 methyl-H), 2.97                                               (singlet, 3 methyl-H), 3.30                                                    (quartet, 4 methylene-H), 4.25                                                 (doublet, 2 allyl-H), 6.61                                                     (doublet of triplets, 1 vinyl-H),                                              7.01 (multiplet, 20 phenyl-H) ppm.                              ______________________________________                                    

PREPARATION EXAMPLE 2

The procedure was as described in Preparation Example 1, with the difference that sodium tetra-p-chloro-phenylborate was used instead of sodium tetraphenylborate.

    ______________________________________                                         Yield         15.4 g (75.6% of theory) of the                                                compound of the abovementioned                                                 formula (2)                                                      Molecular weight                                                                             1018                                                             Melting point 63-64° C.                                                 Elemental anaylsis                                                                           calculated 3.1% H, 1.4% N, 1.1% B,                                             13.9% Cl,                                                                      found 3.4% H, 1.5% N, 1.1% B,                                                  14.5% Cl, 0.07% H.sub.2 O                                        1H-NMR (in DMSO-d6)                                                                          1.23 (triplet, 6 methyl-H), 3.01                                               (singlet, 3 methyl-H), 3.36 (quar-                                             tet, 4 methylene-H), 4.28 (doublet,                                            2 allyl-H), 6.63 (doublet of trip-                                             lets, 1 vinyl-H), 7.04 (multiplet,                                             16 p-chlorophenyl-H) ppm.                                        ______________________________________                                    

PREPARATION EXAMPLE 3

The procedure was as described in Preparation Example 1, with the difference that sodium tetra-p-toluylborate was employed instead of sodium tetraphenylborate and the solvent was replaced by isopropanol/water (1:1 parts by volume).

    ______________________________________                                         Yield         11.5 g (61.2% of theory) of the                                                compound of the abovementioned                                                 formula (3)                                                      Molecular weight                                                                             936                                                              Melting point 151-152° C.                                               Elemental analysis                                                                           calculated 4.7% H, 1.5% N, 1.2% B                                              found 5.0% H, 1.9% N, 1.2% B,                                                  0.07% H.sub.2 O                                                  1H-NMR (in DMSO-d6)                                                                          1.21 (triplet, 6 methyl-H), 2.15                                               (singlet, 3 toluylmethyl-H), 2.97                                              (singlet, 3 methyl-H), 3.33                                                    (quartet, 4 methylene-H), 4.23                                                 (doublet, 2 allyl-H), 6.60 (partly                                             overlapped doublet of triplets, 1                                              vinyl-H), 6.88 (multiplet, 16 p-                                               toluyl-H) ppm.                                                   ______________________________________                                    

PREPARATION EXAMPLE 4

The procedure was as described in Preparation Example 1, with the difference that sodium tetrafluoroborate was employed instead of sodium tetraphenylborate.

    ______________________________________                                         Yield         12.3 g (95.0% of theory) of the                                                compound of the abovementioned                                                 formula (4)                                                      Molecular weight                                                                             648                                                              Melting point 202° C.                                                   Elemental analysis                                                                           calculated 2.5% H, 2.2% N, 1.7% B                                              found 2.7% H, 2.3% N, 1.8% B, 0.5%                                             water                                                            1H-NMR (in DMSO-d6)                                                                          1.24 (triplet, 6 methyl-H), 3.02                                               (singlet, 3 methyl-H), 3.37                                                    (quartet, 4 ethyl-H), 4.28 (doub-                                              let, 2 allyl-H), 6.63 (doublet of                                              triplets, 1 vinyl-H), ppm.                                       ______________________________________                                    

PREPARATION EXAMPLE 5

7.8 g (0.012 mol) of the compound (19) are dissolved in 200 ml of hot isobutanol. 100 ml of water are then added and 4.1 g (0.012 mol) of sodium tetraphenylborate are then slowly added, while stirring. The mixture is stirred vigorously for 1 hour and the product is then filtered off with suction, washed with isobutanol/water (1:1 parts by volume) and then washed with water and dried at 50° C. in vacuo.

    ______________________________________                                         Yield          9.1 g (89.7% of theory) of the                                                 compound of the abovementioned                                                 formula (11)                                                    Molecular weight                                                                              845                                                             Melting point  163° C.                                                  Elemental analysis                                                                            calculated 55.4% C, 3.5% H, 1.7%                                               N, 1.3% B, 38.2% F                                                             found 55.2% C, 3.3% H, 1.6% N,                                                 1.2% B, 36.8% F, 0.19% water                                    1H-NMR (in DMSO-d6)                                                                           3.25 (multiplet, 2 methylene-H),                                               4.97 (triplet, 2 methylene-H),                                                 7.00 (multiplet, 20 phenyl-H),                                                 8.59 (multiplet, 5 pyridyl-H), ppm.                             ______________________________________                                    

PREPARATION EXAMPLE 6

11.1 g (0.017 mol) of the compound of the abovementioned formula (19) are dissolved in 400 ml of hot water, and 1.9 g (0.017 mol) of sodium tetrafluoroborate are then slowly added, while stirring. The mixture is stirred vigorously for 1 hour, the product is filtered off hot with suction, washed with hot water and dried at 50° C. in vacuo.

    ______________________________________                                         Yield         8.7 g (83.5% of theory) of the                                                 compound of the abovementioned                                                 formula (12)                                                     Molecular weight                                                                             613                                                              Melting point 169° C.                                                   Elemental analysis                                                                           calculated 29.4% C, 1.5% H, 2.3% N,                                            1.8% B                                                                         found 29.5% C, 1.6% H, 2.4% N,                                                 1.5% B, 0.06% H.sub.2 O                                          1H-NMR (in DMSO-d6)                                                                          3.21 (multiplet, 2 methylene-H),                                               5.03 (triplet, 2 methylene-H),                                                 8.64 (multiplet, 5 pyridyl-H) ppm.                               ______________________________________                                    

The individual compounds and compound mixtures of the abovementioned formulae (5) to (10) and (13) and (14) were obtained analogously. 

We claim:
 1. An ammonium compound of the formula (I) ##STR14## in which at least one of the radicals R₁ to R₄ denotes a straight-chain fluorine-containing unsaturated and/or saturated alkyl radical having 4 to 30 carbon atoms and not more than three of the radicals R₁ to R₄ independently of one another denote hydrogen atoms or straight-chain or branched alkyl or hydroxyalkyl radicals having 1 to 30 carbon atoms, and R₅ to R₆ denote phenyl, p-chlorophenyl, p-fluorophenyl, p-toluyl, or naphthyl radicals or fluorine atoms.
 2. A compound of the formula (I) as claimed in claim 1, in which at least one of the radicals R₁ to R₄ denotes a straight-chain fluorine-containing unsaturated and/or saturated alkyl radical having 4 to 14 carbon atoms and not more than three of the radicals R₁ to R₄ independently of one another denote straight-chain or branched alkyl(C₁ -C₄) or hydroxyalkyl(C₁ -C₄) radicals, and R₅ to R₈ denote phenyl, naphthyl, p-chlorophenyl, p-toluyl radicals or fluorine atoms.
 3. A compound of the formula (I) as claimed in claim 1, in which at least one of the radicals R₁ to R₄ denotes the group --CH₂ --CH═CF--Rf (Rf=C₅ F₁₁ --C₁₁ F₂₃), the group --CH₂ --CH═CF--C_(n) F_(2n+1), where n=5, 7 or 9, or the group --CH₂ --CH═CF--C₇ F₁₅, and not more than three of the radicals R₁ to R₄ independently of one another denote a methyl, ethyl, butyl or hydroxyethyl group.
 4. A compound or mixture of compounds of the formula ##STR15##
 5. A compound or mixture of compounds of the formula ##STR16##
 6. A compound or mixture of compounds of the formula ##STR17##
 7. A compound or mixture of compounds of the formula ##STR18##
 8. A compound or mixture of compounds of the formula ##STR19##
 9. A compound or mixture of compounds of the formula ##STR20##
 10. A compound or mixture of compounds of the formula ##STR21##
 11. A compound or mixture of compounds of the formula ##STR22##
 12. The compound of the formula ##STR23##
 13. The compound of the formula ##STR24## 